2-Nitrophenylhydrazines

ABSTRACT

2-Nitrophenylhydrazines of the formula   WHEREIN X1 represents nitro, halogeno or trifluoromethyl, X2 represents hydrogen halogen, trifluoromethyl, lower alkyl, carbamyl, lower alkylsulfonyl, lower alkylsulfonamido, lower alkyl carbamyl, lower alkylcarbazyl, carboxyl, lower alkoxycarbonyl, nitro, or cyano, EACH OF R1 and R2 is lower alkyl or lower alkoxy-lower alkyl, or R1 and R2 taken together with the nitrogen atom to which they are linked, represent piperidino, hexamethylenimino, morpholino, or 4-methylpiperazino, and R3 represents hydrogen or lower alkyl, WITH THE PROVISO THAT NO MORE THAN ONE OF X1 and X2 may represent nitro, are herbicidally active compounds. They are toxic to a wide variety of weed species but, at the same time, are not harmful to desirable plant growth. A method for controlling undesirable plants using these compounds and compositions containing these compounds as active ingredients are also disclosed herein.

Unite States Patent [191 Wilcox Z-NITROPHENYLHYDRAZINES Merrill Wilcox, 2911 NW. 30th Ter., Gainesville, Fla. 32601 22 Filed: Aug. 21, 1972 21 Appl. NO.I 282,637

Related US. Application Data [63] Continuation-in-part of Ser. No. 102,993, Dec. 30,

1970, abandoned.

[76] Inventor:

[56] References Cited UNITED STATES PATENTS 3,383,409 5/1968 Bream et al. 260/569 X Primary Examiner-Robert V. Hines Attorney, Agent, or Firm-llarry Falber; Philip P. Berestecki [57] ABSTRACT Z-Nitrophenylhydrazines of the formula [451 Feb. 18,1975

. R3 R W I, x, N

wherein X represents nitro, halogeno or trifluoromethyl, X represents hydrogen halogen, trifluoromethyl, lower alkyl, carbamyl, lower alkylsulfonyl, lower alkylsulfonamido, lower alkyl carbamyl, lower alkylcarbazyl, carboxyl, lower alkoxycarbonyl, nitro, or cyano, each of R and R is lower alkyl or lower alkoxy-lower alkyl, or R and R taken together with the nitrogen atom to which they are linked, represent piperidino, hexamethylenimino, morpholino, or 4-methylpiperazino, and R represents hydrogen or lower alkyl, with the proviso that no more than one of X and X may represent nitro, are herbicidally active compounds. They are toxic to a wide variety of weed species but, at the same time, are not harmful to desirable plant growth. A method for controlling undesirable plants using these compounds and compositions containing these compounds as active ingredients are also disclosed herein.

8 Claims, N0 Drawings 1 Z-NITROPHENYLHYDRAZINES RELATED APPLICATION wherein X, represents nitro, halogeno or trifluoromethyl,

X represents hydrogen halogen, trifluoromethyl, lower alkyl, carbamyl, lower alkylsulfonyl, lower alkyl sulfonamido, lower alkyl carbamyl, lower alkylcarbazyl, carboxyl, lower alkoxycarbonyl, nitro,

or cyano,

each of R, and R is lower alkyl or lower alkoxy lower alkyl, or

R and R taken together with the nitrogen atom to which they are linked, represent piperidino, hexamethylenimino, morpholino, or 4- methylpiperazino, and i R represents hydrogen or lower alkyl, with the proviso that no more than one of X and X may represent nitro.

In the foregoingdefinition,the word lower as used in the terms lower alkyl" and "lower alko xy" indicates sautrated aliphatic hydrocarbon radicals having no more than four carbon atoms. Included within the definition, therefore, are methyl, ethyl, isopropyl, nbutyl, etc., as well as their oxygen-containing analogues. Halogen-containing substituents are those in which the halogen atoms may be fluorine, chlorine, or bromine.

Especially useful are those compounds included within formula (I) which have the structure wherein X represents trifluoromethyl chloro, lower alkyl,

lower alkylsulfonyl. or cyano.

each of R and R represents lower alkyl, and

R is defined as in formula (I).

Particularly useful compounds falling within the structure of formula (II) are those in which X is trifluoromethyl and R is hydrogen.

The following compounds are exceptionally useful in the control of tobacco suckers: 2-(4-chloro-2,6- dinitrophenyl)-l,l,-diethylhydrazine, 2-(2,6-dinitro-4- trifluoromcthyl )-l ,l-diethylhydrazine, 2'( 2- trifluoromethyl,4,6-dinitrophenyl )-l ,l -diethylhydraline, 2-( 2,6-dinitro-p-tolyl)- l ,l -diethylhydrazine, 2-(4- chloro-2,6-dinitrophenyl)-l,l-dimcthylhydrazine, and 2-(2,6-dinitro-4-trifluoromethylphenyl)-l,l-dimethylhydrazine.

The herbicidal compounds of the present invention can ofcourse be formulated and applied in accordance with a wide variety of conventional agronomic techniques. Conveniently herbicidal formulations are prepared containing about 2 percent by Weight active ingredients and are applied at a rate of about 0.5 -30 lbs. per acre. When the compounds of the present invention are used for tobacco sucker control they are preferably applied at a rate of about 10 to about 400 milligrams per plant. I

Compounds of formula (I) may be prepared by reacting substantially equimolar amounts of a 2-nitro-lchlorobenzene of formula (III) (III) X ---Cl with a hydrazine of formula (IV) R 1 (IV) -N in the presence of an acid acceptor such as an alkylamine of formula (V) YgN In these structures, X X R [R and R have the meanings ascribed to them in formula (I), and Y represents lower alkyl. These reactants are dissolved in a suitable aprotic solvent, such as tetrahydrofuran, a dioxane, or low molecular weight ethers. A precipitate of trialkylaminehydrochloride appears and is filtered off. The solvent is then evaporated to yield the 2-nitrophenylhydrazine of formula (I).

The starting materials are readily available or can be preparedby methods well-known in the art. Thus, compounds offormula (III) may be prepared by nitration of an appropriate chlorobenzene or replacement of the -OH group of a nitrophenol by a chlorine atom. Dctails concerning the preparation of a nitrophenol by a chlorine atom. Details concerning the preparation of representative examples of those compounds may be found in Bunnet et al., J.A.C.S 76, 3936-39 (1954), Friedrich et al., US. Pat. No. 2,257,093 (Sept. 30, 1944); and Soper US. Pat. No. 3,442,639 (May 6, 1969).

The hydrazines of formula (IV) are either commercially available or may be prepared by amination of dialkylamines with chloramine or hydroxylamine-O- sulfonic acid or catalyzed ammonia or by reduction of dialkylnitrosamines.

The trialkylaminc of formula (V) functions as an acid acceptor. In lieu thereof, other compounds which will form an insoluble salt in the reaction may be use d.

These compounds include pyridines and alkylpyridines, alkali metal hydroxides, excess substituted hydrazine, or other acid acceptors well-known in the art, It is advantageous to use excess hydrazine as the acid acceptor, since the resulting hydrazine hydrochloride may be treated with an inorganic base, thus recovering the substituted hydrazine.

The Z-nitrophenylhydrazines of formula I, mixed together with the usual additives, are used as herbicidal agents. Furthermore, the active substances can be mixed with fertilizers and applied in this form. The range of activity of the compounds of the invention can be widened by applying them in admixture with other herbicides, e.g., with triazines such as halogendiaminos-triazines, alkoxyand alkylthiodiamino-s-triazines, diazines such as uracils, pyridazines, phenols, aliphatic carboxylic acids and halogen carboxylic acids, halogenated benzoic acids and halogenated phenylacetic acids, aryloxyalkane carboxylic acids and aryloxyalkane sulfonie acids, pyridine carboxylic acids, amides, thioamides, hydrazides, esters and nitriles of similar carboxylic acids, carbamic acid esters and thiocarbamic acid esters, quaternary ammonium compounds, ureas, inorganic salts, etc., especially with: 2-chloro-4,6-bis-(ethylamino)-s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chlo ro-4,6-bis-(methoxypropylamino)-s-triazine 2-methoxy-4,6-bis-(isopropylamino)-s-triazine 2-methylthio-4-methoxypropylamino-isopropylamino-s-triazine 2-methylthio-4,6-bis-(isopropylamino)-s-triazine 2-methylthio-4,6-bis-ethylamino)-s-triazine 2-mjethylthio-4-ethylamino-6-isopropylamine-striazine 2-methoxy-4,6-bis-(ethylamino)-s-triazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis-(isopropylamino)-s-triazine 5-br0mo-3-sec.butyl--methyl-uracil 3-cyclohexyl-5,6-trimethylene-uracil S-aminO-S-chloro-l-phenyl-pyridazone-(6) 3,6-dioxo-l ,2,3,6-tetrahydropyridazine dinitro-sec.butylphenol and salts thereof pentachlorophenol and salts thereof trichloroacetic acid and salts thereof 2,2-dichloropropionic acid and salts thereof 2-chloro-N,N-diallylacetic acid amide N-(3,4-dichlorophenyl)-cyclopropane acid amide maleic acid hydrazide 2,3,6-trichlorobenzoic acid and salts thereof 2,3,5,6-tetrachlorobenzoic acid and salts thereof 2-methoxy-3,5,6-trichlorobenzoic acid and salts thereof 2-methoxy-3,6-dichlorobenzoic acid and salts thereof carboxylic '2-(2',4,5'-trichlorophenoxyfip'ropionic acid and" salts and esters thereof 2-(2,4,5'-trichlorophenoxy)-ethyl-2,2

dichloropropionate 4-(2',4'-dichlorophenoxy)-butyric acid and salts and esters thereof 4-(2'-methyl-4-chlorophenoxy)-butyric acid and salts and esters thereof 2,3,6-trichlorobenzyloxypropanol 4-amino-3,5,6-trichloropicolinic acid N'-cyclooctyl-N,N-dimethyl urea 3-phenyll ,l-dimethyl urea 3-(4-chlorophenyl)-l .l-dimethyl urea 3-(3'-trifluoromethylphenyl)-l l -dimethyl urea 3-(3,4'-dichlorophenyl)-1,l-dimethyl urea 3-(3',4-dichlorophenyl)-l-n-butyl-l-methyl urea 3-(3',4-dichlorophenyl)- l ,l ,3-trimethyl urea 3-(3 ,4-dichlorophenyl)-l ,l-diethyl urea 3-(4-chlorophenyl)-l -methoxy-l-methyl urea 3-(3,4'-dichlorophenyl)-l-methoxy-l-methyl urea 3-(4-bromophenyl)-methoxy-l methyl urea 3-(3',4-dichlorophenyl)-3-methoxy-l,l-dimethyl urea I 3-(4-chlorophenoxyphenyl)-l,l-dimethyl urea N,N-di-(n-propyl)-S-ethyl-thiolcarbmaic acid ester N,N-di-(n-propyl)-S-n-propyl-thiolcarbamic acid ester N-ethyl-N-(n-butyl)-S-thiolcarbamic acid ester N-phenyl-O-isopropyl-carbamic acid ester N-(m-chlorophenyl)-O-isopropyl-carbamic acid ester N-(m-chlorophenyl)-O-(4'-chloro-2-butinyl)- carbamic .acid ester N-(3,4-dichlorophenyl)-O-methyl-carbamic acid ester.

The following examples are intended to illustrate some of the embodiments of the present invention The examples therefore are for illustrative purposes only and are not to be construed as limitations.

EXAMPLE 1 Equimolar amounts of 4-chloro-3,5-dinitrobenzotrifluoride, l,l-diethylhydrazine, and triethylamine were dissolved in tetrahydrofuran in that order. A precipitate of triethylamine hydrochloride appeared. After a few days, the precipitate filtered off and the solvent evaporated to yield crude 2-(2',6'-dinitro-4'- trifluoromethylphenyl)- l l -diethylhydrazine, m.p. 68-75C. Recrystallization from hexane gives m.p. 8284C.

Analysis C H F N O Cale. C. 40.99%; H, 07%; N. 17.39% Found C. 40.78%; H, 4.08%, N. 17.37%.

EXAMPLE 2 Six grams of 4-chlorophenylmethylsulfone plus 3.3 grams potassium nitrate were dissolved in 50 ml 30 percent fuming sulfuric acid, heated to 90C, then cooled. More potassium nitrate (6.6 grams) was then added, and the mixture heated to 120-140C for five hours, cooled, and poured over ice. Seven grams of crude 4- chloro-3,5-dinitrophenylmethylsulfone, m.p. 190-200C. were recovered. The latter is reacted with 1,1-diethy1hydrazine and triethylamine as in Example 1 to give crude 2-(2',6-dinitro-4- methylsulfonylphenyl)1.l-diethylhydrazine, m.p. 139-144C. Recrystallization from tetrahydrofuran and ligroine gives m.p. 153.5 154.5C.

Analysis C H N O S Calc. C. 39.75;H. 4.851N. 16.86. Found C. 39.841H. 5.04; N. 16.74.

EXAMPLES 3 36 The methods of Example 1 were used, employing the proper reactants, to prepare a number of Z-nitrophenyl-hydrazine compounds according to formula (1). These compounds, together with their crude melting points, appear in the following table:

TABLE l Compound m.p.

3 2(2.6'-dinitro-4'-trifluoromethylphenyl 1-1 .l-dimethylhydrazine 106-107C (Hexane) Analysis- C H F N.O. Cale. C. 36.74; N. 19.05 Found C. 36.89; N. 19.15 4 2-(2'.6'-dinitro-4-trifluoromethy1- phenyl1-1.1.Z-trimethylhydrazine Analysis- C H F N 0, Ca1c.C. 38.97; N. 18.18 Found C. 39.11; N. 18.02 5 2(2.6-di nitro 4'-trifluoromethy1- phenyl1-1.l-dimethyl-2-n-propylhydrazine 6 2-(2'.6-dinitro-4'-trifluoromethylphenyl1-1,1-dimethyl-2-isopropylhydrazine 7 2-12'.6-dinitro-4'-trifluoromethylphenyl )-1,1-dimethyl-2-cyc1opentylhydrazine 8 2-(2',6'dinitro-4"trifluoromethylphenylrl.l-di-n-butylhyrazine 9 2-(2,6-dinitro-4-trif1uromethylphenyl)1,l-di-n-propylhydrazine 2(2'.6'-dinitro-4'-trifluoromethylphenyl l l -diisopropylhydrazine 2-(2'.6'-dinitro-4'-trifluoromethy1- phenyl 1 -n-buty1- l-ethylhydrazine 12 1-(2.6'-dinitro-4'-trifluoromethylanilinol-hexamethylenimine Analysis- C H F;. N 0,, Cale. C. 44.83; N. 16.09 Found C. 45.16; N, 16.10 1-(2'.6-dinitro-4-trif1uoromethylani1ino)-piperidine Analysis- C H F N 0, Calc. C. 43.12; H, 3.92; N, 16.76 Found C. 43.11; H. 3.92; N. 16.73 4-(2.6'-dinitro-4'-trifluoromethylanilino)-morpholine Analysis-- C H, F. N. Calc. C, 39.29; H, 3.30; N, 16.66 Found C, 39.26; H, 3.31; N, 16.62 2-( 2 ',6-dinitro-p-tolyl)-1.1-diethylhydrazine Analysis- C H N. 0 Calc. C, 49.25; H. 6.01; N, 20.89

red oil red oil red oil red oil red oil red oil TABLE l-Continued Ex. Compound Found C. 49.21; H, 5.97; N. 20.71 2(2',6-dinitro-4- :yanophenyl)-1.1

diethylhydrazine Analysis C H N. O, Ca1c.C. 47.31; N. 25.08 Found C. 47.19; N, 25.14 2-(2'-ch1oro-4.6'-dinitrophenyl)-1.l-

diethylhydrazine Analysis m H N 0 Cale. C, 41.61; H. 4.54; N, 19.41 Found C, 41.79; H, 4.58; N. 19.34 2-(2-trifluoromethyl-4.6'-dinitrophcnyl 1 1 -diethylhydrazine 2-(4'-chloro-2',6"dinitrupheny11-1.1-

diethylhydrazine Ana1ysis Cm H C1N O. Calc. C. 41.61. H. 4.54; N, 19.41 Found C. 41.73; H, 4.55; N. 19.27 2-(4-methoxycarbonyl-2.6'-dinitropheny1)-l,l-diethylhydrazine Analysis- C H... N ,O Cale. C, 46.15; N. 17.94 Found C, 46.52; N. 17.92 21 2 (4'-dimethylcarbamyl-2',6-dinitrophenyl)-1,l-diethylhydrazine Analysis C H N 0 Cale. C, 47.99; N, 21.53 Found C, 48.19; N, 21.67 2-(4'-(dimethylaminosulfonyl)-2'.6-

dinitrophenyl)-l ,1diethylhydrazine 2-(4'-(trimethylhydrazinosulfonyl)-2',

bdinitrophenyl l 1 -diethylhydrazin 2-(4'-(2.2-dimethy1hydrazinosulfonyl) -2.6'-dinitropheny1)-l.l-diethylhydrazine 2(4-(aminosulfonyl)2,6-dinitrophenyU-1.1-dicthylhydrazine 2-(4'-(N,N-dimethy1carbazyl)-2'.6

dinitrophenyl)-1,1-diethy1hydrazine 2-(4'-(N.N,N-trimethylcarbazyl1-2.

6-dinitrophenyl) l.l-diethylhydrazine Ana1ysis C H N 0 Calc. C. 47.45; N. 23.72 Found C, 47.60; N, 23.73 2-(4-(N,N-dimethy1carbazyl)-2,6'-

dinitrophenyl 1 1 -dimethy1hydrazine 2-(4-carbamyl-2.6"dinitropheny1) -1,1diethy1hydrazine 2-(4'-carbazy1-2.6-dinitrophenyl) -1,1-diethylh vdrazine 2-(4-(2.2-diethylcarbazy1)-2',6-

dinitrophenyl 1 l-diethylhydrazine 32 2-(4'-(Nmethoxy-N-methylcarbamy'l1-2,

6-dinitrophenyl)-1,1'diethy1- hydrazine Analysis- C H N 0,, Calc. C, 45.74; N. 20.52 Found C. 45.73; N. 20.40 2-(4'(2.2-dimethylhydrazinosulfonyl -2'.6'-dinitrophenyl-1,l-dimethylhydrazine 2(4-(2,2-diethylhydrazinosulfonyl) 2',6-dinitropheny1)- 1 ,l-diethylhydrazine 2-(4'-chloro-2.6-dinitrophenyl)-1,1-

dimethylhydrazine Analysis- C C C1 N. 0 Calc. C. 36.86; N, 21.50 Found C. 36.88; N. 21.58 2-(2',6-dinitrophenyl1-1.ldiethy1- hydrazine Analysis C H N, O, Calc. C. 47.24; H. 5.51; N. 22.04 Found C. 47.37; H. 5.51; N. 22.00

red oil red oil EXAMPLE 37 Various Z-nitrophenylhydrazine derivatives prepared according to the foregoing examples were finely ground in potassium bromide, suspended in 0.1% aqueous lgepal CO-89O non-ionic surfactant and applied at a rate of 10 lbs. per acre to various weed and crop species. The seeds were pushed into the soil surface and left exposed until soon after application of the Z-nitrophenylhydrazines, at which time they were covered with a thin layer of soil. The tests were conducted in a carrier control was prepared in the same way. These compositions were applied at the rate of 5 lbs. of active ingredient per acre to various crop and weed species.- The seeds were pushed into the soil surface and the surface was treated with the aforementioned compositions. Eighteen hours after treatment, the seeds were covered with a thin layer of soil. These tests took place in a greenhouse with the enhanced lighting described in Example 16. Ten days after treatment, the stand and vigor as a percent of the untreated control were observed. The data are set forth below in Table Ill.

TABLE ll Compound Ryegrass Coker 67 Corn Annual Bluegrass Rutgers Tomato of Example No. Lvlium mulliforum Zea mays Poa Annun Lycopersicum esculemmn 3 stand (7L 100 0 100 vigor "/1 0 70 0 SO 4 stand 7/. 0 7O 0 100 vigor '7r/ 0 70 0 8O stand '71. 80 100 I00 100 vigor '/1. 60 I00 20 100 trifluralin stand "/1. 0 90 100 I00 vigor '71. 0 20 5O 5O Carrier stand '71 I00 I00 lOO 100 Control vigor 75 lOO 100 I00 100 Check stand /r lOO 100 100 l00 (untreated) vigor "/1 lOO l00 100 100 TABLE III Giant Grey Stripe v Rutgers Tomato Florida Broad Leaf Compound Rye grass Coker 67 Corn Sunflower Mustard 0f Lolium Lycopersimn Example No. mulliforum Zea mays Helium/ms amumx est'ulenlum Bruszricu juncea stand 7: O 80 100 80 80 l vigor 7r 0 5 60 10 stand 0 100 100 50 8O trifluralin I vigor 7i: 0 l0 2O 2O Carrier stand 7: 100 100 l00 100 100 Control vigor 7a 100 100 100 I00 100 stand I00 100 100 lOO 100 Check (untreated) vigor 7:. l0() I00 100 I00 100 EXAMPLE 38 EXAMPLE 39 thoroughly blended. A solution of trifluralin and of the Compositions containing various compounds of this invention were prepared according to the method disclosed in Example 38. They were applied to various species of crops and weeds according to the method of Example 38 except that the application rate was 1 lb.

per acre. Nine days after treatment, the stand and vigor as a percent of the untreated control were observed. The data are recorded in Table IV.

TABLE IV Giant Grey Stripe Rutgers Tomato Florida Broad Leaf Compound Ryegrass Coker'67 Corn Sunflower Mustard of Lolium l. -npt'r.titwn Example No. mulllfurum Zt'u mu \'.s' Helium/tux mmm' t'xt'ult'nmm HIUA'Slt'lI jum't'u I stand 71 0 I00 llll) llli) I00 vigor '7: (l 5 I00 50 2t) 9 stand 7r 0 I00 100 l()() l(l() vigor 7r 6 9O 60 IO stand 70 40 100 l0() 4() I00 vigor 70 100 90 7t) 70 l I stand 70 5 100 lOO 40 I00 vigor 7a 40 (10 7O Trifluralin stand "/n 0 l0() I00 50 30 vigor "/0 O 20 4O 30 IO Carrier stand '70 I00 I00 I00 I00 Control vigor '/r 100 100 I00 100 100 Check stand 70 I00 100 100 l()() 100 (untreated) vigor lOO lOO lOO lOO I00 EXAMPLE 40 TABLE triazine). The data obtained are reported below in Table VI.

EXAMPLE 42 An experiment was performed as in Example 37, except that the compounds were applied at 2 lb. per acre and ratings were made in ten days. The data obtained are reported in Table VII.

Giant Grey Stripe Rutgers Tomato Florida Broad Leaf Compound Ryegrass Coker 67 Corn Sunflower Mustard Lnliunl L \'mpur.\'imn Example No. mulrlfurmn ZL'U nu'lyx Helium/ummums tflt'tllltllllllll Brmzvicu jlllll't'U 3 stand "/1 I00 I00 (l 40 vigor "/1 80 80 0 40 I3 Stand 7( 30 I00 I00 40 I00 vigor 7! 60 I00 80 60 70 14 stand 71 50 I00 I00 70 I00 vigor /0 80 I00 I00 70 80 I0 stand 7r 0 I00 I00 I0 50 vigor 7i. 0 l0 I0 20 5 l I stand "/1 0 80 I00 20 I00 vigor 7r 0 70 90 2O 70 Trifluralin stand 0 I00 I00 I00 I00 vigor 7c 0 I0 20 3O I0 Carrier stand 70 I00 I00 I00 I00 100 Control vigor I00 I00 I00 I00 I00 Check stand 71 I00 I00 100 I00 I00 (untreated) vigor 7r I00 I00 I00 I00 I00 EXAMPLE 4] EXAMPLE 43 Various 2-nitrophenylhydrazine derivatives were finely ground with potassium chloride, suspended in a GI percent aqueous Igepal CO-890 non-ionic surfactant. The seeds were pushed into the soil surface and the herbicidal compositions were applied at a rate of 2 lbs. ofactive ingredient per acre. These tests took place An experiment was performed as in Example 42. The data obtained are reported in Table VIII.

EXAMPLE 44 An experiment was performed as in Example 37 except the compounds were applied in an aqueous solution containing 25 percent methanol and 0.1 percent Igepal CO-890 non-ionic surfactant. Ratings made ten clays later appear in Table IX.

EXAMPLE 45 An experiment was performed as in Example 44, except that ratings were made in four days. The data obtained are reported in Table X.

TABLE VI Giant Grey Stripe Rutgers Tomato Florida Broad Leaf Compound Ryegrass Coker 67 Corn Sunflower Mustard 0f Loliuni L \'c0per5ic0n Example No. multrforum Zea mays Helium/ms annuus esculenmm Brussica junr'eu 3 stand 5 I00 I00 I00 vigor I0 80 I00 20 I stand 7: 0 I00 I00 30 20 vigor 7r 0 20 I00 5 5 16 stand 7: 20 I00 I00 I00 I00 vigor 80 90 I00 80 8O 2 stand I0 I00 I00 40 80 vigor 7r 25 I00 I00 10 3O Trifluralin stand 0 I00 I00 25 vigor 0 5 I0 5 5 Atrazine stand 5 I00 5 I0 vigor I0 I00 I0 5 5 Carrier stand 70 I00 I00 I00 I00 I00 Control vigor I00 I00 I00 I00 I00 Check stand 7c I00 I00 I00 I00 I00 (untreated) vigor I00 I00 I00 I00 I00 EXAMPLE 46 Untreated Check 400 ppm 1400 ppm 4000 ppm EXAMPLE 47 An experiment was performed, as in Example 46, except that ml. of 50 percent acetone in water containing 267, 911, or 2,670 parts of 2-(2,6-dinitro-4- trifluoromethyl)-l,l-diethylhydrazine was applied Percentages of suckers were as follows:

Untreated Check 267 ppm 9| l ppm 2670 ppm EXAMPLE 48 An experiment was performed, as in Example 47, except that 2-(2-chloro-4,o-dinitrophenyl)-l ,l-dicthylhydrazine was the solute. Percentage of suckers were:

267 ppm Untreated Cheek 91 1 ppm 2670 ppm EXAMPLE 49 An experiment was performed in the manner of Example 46, except that A-820 (the known herbicide and tobacco sucker agent 4-t-butyl-2,6-dinitro-N-secbutylaniline) and the compound of Example 19 were each applied to 8 plants to 2667 ppm. Suckers were counted 28 days later:

No. Suckers/8 plants check 44 A-820 2 Example 19 1 EXAMPLE 50 An experiment was conducted as described in Example 49, except the compounds of Examples 1 and 17 were tested:

No. suckers/8 plants carrier control 50 Example 17 22 Example 1 6 The compounds of the present invention are especially desirable for controlling tobacco suckers in that the treatment does not damage the tobacco and obviates much hand labor. They are also advantageous because they are unusually soluble in organic solvents,

The production of herbicidal compositions according to the invention is carried out in a manner well-known in the art by the intimate mixing and grinding of the active substances of the general formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can exist and be used in the following forms: i

as solids: dusts, sprinkling agents, granulates, coated granules, impregnatedgranules and homogeneous granules;

as concentrates of active substances dispersible. in

water: wettable powder, pastes, emulsions;

as liquids: solutions, aerosols.

To produce the solid forms (dusts, sprinkling agents, granulates), the active substances are mixed with solid carriers. Suitable carriers are, e.g.., kaolin, talcum, bole, chalk, limestone, ground limestone, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminum silicates (feld-;

spar and mica), calcium and magnesium sulfates, magnium nitrate, ureas, ground vegetable products such as grain flour, bark flour, sawdust, ground nut shells, cellulose powder, residues of plant extractions, activated charcoal, etc.. These carriers can be used separately or they can be mixed with each other.

The grain size of the carriers is, for dusts, advantageously up to ca. 0.1 mm, for sprinkling agents it is ca. 0.075 to 0.2 mm and for granulates 0.2 mm upwards.

The concentrations of active substances in the solid preparations are, as a rule, 0.5 to percent olthe total weight.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionactive and cation-active substances, which, for example, improve the adhesion ofthe active substances on plants and parts of plants (glues and adhesives) and/or ensure a better wettability (wetting agents) and also dispersibility (dispersing agents). The following are examples of adhesives: olein-chalk mixtures, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoand di-alkyl phe nols having 5 to 15 ethylene oxide radicals per molecule and eight or nine carbon atoms in the alkyl radical, lignin sulfonic acids, their alkali and alkaline earth metal salts, polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and eight to 18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea/formaldehyde as well as Latex products.

Concentrates of active substances which can be dispersed in water (wettable powders), pastes and emulsion concentrates. are agents which can be diluted with water to given any desired concentration. They consist of active substances, carriers, optionally additives which stabilize the active substance, surface agent substances and antifoaming agents and, optionally, solvents. The concentration of active substance in these agents is 5 to 80 percent of the totall weight of the latter.

The wettable powders and pastes napthalene obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable devices until homogeneity is attained. Suitable carriers'are, for example, those previously mentioned for solid preparations.- It is advantageous in some cases to use'mixtures of different carriers. Suitable dispersing agents are, e.g., condensation products of sulfonated The active substances are so mixed, ground, sieved and strained with the above-mentioned additives that the solid'par ticle size in wettable powders does not exceed 0.02 0.04'mm and, in the case of pastes, 0.003 mm.

' To produce emulsion concentrates and pastes, dispersing agents such as those stated in the previous sections, organic solvents and water are used. Examples'of solvents are: alcohols, benzcne, xylenes, toluene, dimethyl 'sulfoxide and mineral oil fractions boiling between 120 and 350C. The solvents must be practically without smell, not phytotoxic, inert to the active substances and not easily flammable. 1

In addition. the agents according to the invention can be used inthe form of solutions. For this application,

the active substance or substances of the general for mula l are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, mineral oils, ontheir own or mixed with each other, can be used as organic solvents. The solvents should contain the active substances within a concentration range of l to 20 percent calculated on the total weight of the resulting solution.

Other biocidal activesubstances or agents can be mixedwith the described compositions according to the invention. Thus. in addition to the stated compoundsof the general formula I and other herbicides, the newage nts can also'contain, e.g., insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nemactocides in order to widen the range of action. The compositions according to the invention can also contain fertilizers, micronutrients, etc.

Forms of preparation of these active substances are described in the following. Where not otherwise expressly stated, the terms parts and percentages are given by weight.

'Wettable Powder The following constituents are used to produce a. a 10 percent wettable powder, and

b. a percent wettable powder:

10 parts of- 2-(2,6-dinitro-4- ftrifluoromethylphenyl )-l ,l-dimethylhydrazine l paprts of lignin sulfonic acid'calcium salt 2 parts of adhesive consisting of 50% polyvinyl.-

pyrrolidone and 50% Champagne chalk 38 parts of kaolin 40 parts of Champagne chalk 25 parts of 2-(2,6-dinitro-4-trifluoromethylphe'nyl 1,1,2-trimethyldrazine 5 parts of condensation products of naphthalene sulfonic acid, phenol sulfonic acids and formaldehyde in the ratio 31220.5

4 parts of dibutyl naphthyl sulfonate sodium salt 1 part of methyl-oleyl-tauride sodium salt 15 parts of silicic acid 25 parts of'neutral sodium aluminum silicate 25 parts of kaolin The stated active substances are coated onto the corresponding carriers (kaolin and chalk) and then mixed and ground with the listed additives. A wettable pow'- der is obtained having excellent wettability and suspension properties. Suspensions of any desired active-substance concentration'can be prepared from this wettable powder by diluting with water.

Emulsion Concentrate The following constituents are mixed together to produce a 25 percent emulsion concentrate:

25 parts of 2-(2,6-dinitro-4-ytrifluoromethylphenyl)-l.,l-diethylhydrazine 35 parts of mcthylcthylketone 30 parts of xylol and I 10 parts of isoo'ctylphenyl polyethylene glycol This concentrate can be diluted with water to obtain emulsions, of suitable concentrations. Such emulsions are suitable for controlling weeds in cultivated plantations, for which purpose application of amounts of about 0.5 to 4 lbs. of a compound of formula (I) per acre of treated soil is recommended. I i

I claim:

l. A compound of the formula 5. A compound according to claim 1 Which'is 2-(2',

propylhydrazine.

6. A compound according to claim l'whic h is 2- (2',6-dinitro-4'-trifluoromethylphenyl)-l-n-butyl lethylhydrazine.

7. A compound according to claim 1 which is 2-(2', 6'-dinitro-4'-trifluoromethylphenyl l l -diisopropylhydrazine. i I

8. A compound according to claim 1 which is 2-(2', 6'-dinitro-4'-chlorophenyl)-l ,l-diethylhydrazine. 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 which is 2-(2'',6''-dinitro-4''-trifluoromethylphenyl)-1,1-diethylhydrazine.
 3. A compound according to claim 1 which is 2-(2'', 6''-dinitro-4''-trifluoromethylphenyl)-1,1-dimethylhydrazine.
 4. A compound according to claim 1, which is 2-(2'', 6''-dinitro-4''-trifluoromethylphenyl)-1,1-2-trimethylhydrazine.
 5. A compound according to claim 1 which is 2-(2'', 6''-dinitro-4''-trifluoromethylphenyl)-1,1-di-n-propylhydrazine.
 6. A compound according to claim 1 which is 2-(2'' ,6''-dinitro-4''-trifluoromethylphenyl)-1-n-butyl-1-ethylhydrazine.
 7. A compound according to claim 1 which is 2-(2'', 6''-dinitro-4''-trifluoromethylphenyl)-1,1-diisopropylhydrazine.
 8. A compound according to claim 1 which is 2-(2'', 6''-dinitro-4''-chlorophenyl)-1,1-diethylhydrazine. 